The present invention relates to particles which are useful as a carrier and a catalyst component for olefin polymerization a catalyst for olefin polymerization using the same, and method for producing an olefin polymer using said catalyst for olefin polymerization.
A lot of reports on a method for producing an olefin polymer using a transition metal compound have already been made. As the example of using a metallocene transition metal compound, for example, Japanese Patent Publication (Kokai) No.58-19309 discloses a method of producing an olefin polymer using bis(cyclopentadienyl)zirconium dichloride and methylaluminoxane. Japanese Patent Publication(kohyo) No.1-502036 discloses a method of producing an olefin polymer using bis(pentamethylcyclopentadienyl)zirconium dimethyl and n-butylammonium tetrakisphenylborate. Japanese Patent Publication(Kokai) No.5-178923 discloses a method of producing an olefin polymer using dimethylsilylbis(2,4-dimethylcyclopentadienyl)zirconium dimethyl, dimethylanilinumtetrakis(pentafluorophenyl)borate and triethylaluminum. Furthermore, a lot of examples using a non-metallocene transition metal compound are disclosed in J. Amer. Chem. Soc., 115, 8493(1993), Plastics Engineering, March. 77(1996), WO96/23010 and the like.
Since catalysts using these transition metal compounds are soluble in a reaction system, when used in the polymerization accompanying formation of polymer particles (e.g. slurry polymerization, gas phase polymerization, etc.), the shape of the formed polymer is irregular to cause formation of large polymer particles, an agglomerate polymer and fine polymer particles, decrease in bulk density of the polymer, adhesion of the polymer to the polymerization reactor wall. Consequently, poor heat transfer and poor cooling in the reactor, and the like are caused, which results in difficulty in stable operation and lowering of the productivity.
In order to apply the transition metal compound to the polymerization accompanying formation of polymer particles (e.g. slurry polymerization, gas phase polymerization), it is necessary that not only sufficient polymerization activity is exerted but also the polymer excellent in shape and particle properties is obtained. To solve these problems, a method of supporting a transition metal compound on a carrier has been proposed.
As one method, for example, a method of fixing or supporting all or a part of a catalyst component such as metallocene complex, methylaluminoxane or the like on an inorganic metal oxide carrier such as silica or the like has been reported.
For example, Japanese Patent Publication(Unexamined) Nos. 60-35006, 60-35007 and 60-35008 respectively disclose a method of depositing/adhering a soluble metallocene on a typical support (e.g. silica, alumina, polyethylene, etc.) to convert into a supported heterogeneous catalyst and using a combination of the catalyst and aluminoxane in the slurry polymerization or gas phase polymerization.
Japanese Patent Publication (Unexamined) No. 61-108610 discloses a method of producing a polyolefin polymer using a solid catalyst component obtained by adding a calcined silica to bis(cyclopentadienyl)zirconium dichloride and a reaction product of trimethylaluminum and water.
Japanese Patent Publication(Unexamined) No. 61-276805 discloses a method of producing an olefin polymer using an inorganic oxide-containing organoaluminum component, obtained by reacting a mixture of methylaluminoxane and trimethylaluminum with silica, and bis(cyclopentadienyl)zirconium dichloride.
Japanese Patent Publication(Unexamined) No. 61-296008 discloses a method of producing an olefin polymer using a solid catalyst containing aluminum and zirconium, obtained by treating silica in turn with methylaluminoxane and bis(cyclopentadienyl)zirconium chloride.
As the improved method, for example, there have been reported a method of using a solid catalyst component obtained by fixing/supporting all or a part of a catalyst component such as metallocene complex, methylaluminoxane, etc. on an in organic metal oxide carrier such as silica, etc., and aluminoxane or organoaluminum, and a method of using a pre-polymerized catalyst obtained by carrying out prepolymerization. Japanese Patent Publication (Kokai) No.63-51407 discloses a method of producing an olefin polymer using a solid catalyst component obtained by treating silica in turn with methylaluminoxane and bis(cyclopentadienyl)zirconium dichloride, and methylaluminoxane.
Japanese Patent Publication (Kokai) No.63-89505 discloses a method of producing an olefin polymer using a solid catalyst component obtained by treating silica in turn with methylaluminoxane and bis(cyclopentadienyl)zirconium dichloride, and triisobutylaluminum or a method of producing an olefin polymer using a solid catalyst component pre-polymerized with the solid catalyst component and triisobutylaluminum.
In the above prior arts, use of aluminoxane is essential. This aluminoxane must be separately synthesized and a lot of steps are required and are complicated. The aluminoxane is unstable and costly. Regarding the solid catalyst component obtained by combining the aluminoxane with an inorganic metal oxide carrier such as silica, the amount of aluminum used is large and activity per 1 mol of an Al atom was low. To solve these problems, there has been reported a method of producing an olefin polymer using a solid catalyst component obtained by reacting an organoaluminum with water in the presence of an inorganic metal oxide carrier such as silica to form aluminoxane.
For example, Japanese Patent Publication (Kokai) No.61-31404 discloses a method of producing an olefin polymer using a catalyst obtained by adding water, trimethylaluminum and bis(cyclopentadienyl)zirconium dichloride in turn to silica.
Japanese Patent Publication (Kokai) No. 1-1207303 discloses a method of producing an olefin polymer using silica gel powders containing a supported metallocene-methylaluminoxane catalyst complex, obtained by adding silica gel not dehydrated, containing water to trimethylaluminum and treating the resultant with bis(n-butylcyclopentadienyl)zirconium dichloride.
Japanese Patent Publication (Kokai) No. 3-234710 discloses a method of producing an olefin polymer using a prepolymerized solid catalyst, obtained by adding water, trimethylaluminum and bis(methylcyclopentadienyl)zirconium dichloride in turn to silica and further adding ethylene to the mixture, and triisobutylaluminum.
According to these prior arts, synthesis of aluminoxane and fixing of the component to an inorganic metal oxide carrier such as silica or the like can be easily and simply performed. However, these methods require control of the amount of water used and it is difficult. Furthermore, the aluminoxane synthesized by this method and the solid catalyst component obtained by fixing the aluminoxane synthesized by this method have low activity, unlike separately synthesized aluminoxane and a solid catalyst component obtained by fixing the separately synthesized aluminoxane, and the particle properties of the resulting polymer are not preferred.
There has been reported a method of producing an olefin polymer using a solid catalyst component obtained from a metallocene transition metal compound, a boron compound and a carrier, or a solid catalyst component obtained from a metallocene transition metal compound, a boron compound, an organoaluminum compound and a carrier.
For example, Japanese Patent Publication (Kohyo) No.5-502906 discloses a method of producing an olefin polymer using a supported catalyst obtained by adding a reaction product of bis(cyclopentadienyl)zirconium dimethyl and N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate to basic alumina.
Japanese Patent Publication (Kokai) No. 6-336502 discloses a method of producing an olefin polymer using a solid catalyst component, obtained from a carrier prepared by treating silica with triethylaluminum, ethylenebisindenyl zirconium dichloride and N,N-dimethylanilinumtetrakis(pentafluorophenyl)borate, and further, triisobutylaluminum.
However, the boron compound used in these prior arts must be separately synthesized and a lot of steps are required and are complicated. Since the amount of the boron compound to be incorporated into a carrier such as silica is usually small and the reaction product of the metallocene transition metal compound and boron compound is generally unstable, the activity in case of polymerizing an olefin using the resulting solid catalyst component was low.
There have recently been reported a method of producing a catalyst for olefin polymerization using an aluminum compound wherein a special group is introduced, in place of aluminoxane and a boron compound, and a transition metal compound, or using them in combination with an organoaluminum compound, and a method of producing an olefin polymer using the same.
For example, Japanese Patent Publication(Unexamined) No. 6-329713 discloses a method of producing an olefin polymer using a solid component of an aluminum compound having an electron attractive group, obtained by reacting trimethylaluminum and pentafluorophenol, and bis(cyclopentadienyl)titanium dichloride. There is also described a method of producing a catalyst component by supporting an aluminum compound, wherein a special group is introduced, on an inorganic carrier or organic carrier. However, there is not disclosed the example of actually supporting the aluminum compound having an electron attractive group obtained by reacting trimethylaluminum with pentafluorophenol, and the polymerization activity in case of using a supported solid catalyst component as described in the publication was low.
Furthermore, there has recently been reported a catalyst for olefin polymerization, composed of a modified clay, obtained by treating a clay mineral with a compound capable of introducing a cation into layers, as a substitute of aluminoxane and a boron compound, a metallocene complex and an organoaluminum compound.
For example, Japanese Patent Publication (Kokai) No.7-224106 discloses a method of producing an olefin polymer using a modified clay obtained by using ferrocene, concentrated sulfuric acid and synthetic high purity montmorillonite, triisobutylaluminum and ethylenebis(indenyl)zirconium dichloride.
However, many clay minerals have irregular shape, particle diameter and particle properties and, moreover, olefin polymers obtained by using the clay minerals, contain a large amount of irregular matters in shape and particle properties. There is described that the modified clay is prepared in an aqueous solution to introduce a cation into layers of the clay mineral, however, water is essentially an inhibitor for olefin polymerization and complete removal of water from the modified clay was required but was difficult.
Under these circumstances, problems to be solved by the present invention, that is, an object of the present invention is to provide particles capable of giving a polymer having excellent shape and particle properties with high activity when a catalyst for olefin polymerization obtained by using a transition metal compound is applied to the polymerization accompanying formation of polymer particles (e.g. slurry polymerization, gas phase polymerization, etc.) by using in combination with the transition metal compound, a carrier consisting of said particles, a catalyst component for olefin polymerization consisting of said particles, a catalyst for olefin polymerization comprising said particles, and a method for producing an olefin polymer by using said catalyst for olefin polymerization.
To accomplish the above object, the present inventors have intensively investigated about a method for producing an olefin polymer with a transition metal compound, particularly a method for producing an olefin polymer according to the polymerization accompanying formation of polymer particles. As a result, the present inventors found modified particles obtained by contacting dry particles with a specific compound, and accomplished the present invention.
The present invention relates to modified particles obtained by contacting dry particles(a) with an organometallic compound(b), and subsequently a compound(c) having a functional group containing an active hydrogen or a non-proton donative Lewis basic functional group, and an electron attractive group.
Further, the present invention also relates to a carrier comprising said particles; a catalyst component for olefin polymerization, comprising said particles; a catalyst for olefin polymerization, comprising said particles(A) and a transition metal compound(B), or an additional organometallic compound(C) therewith; and a method for producing an olefin polymer with said catalyst for olefin polymerization.
The present invention will be explained in detail below.
(a) Dry Particles
The modified particles of the present invention are obtained by contacting dry particles(a) with an organometallic compound(b), and subsequently a compound(c) having a functional group containing active hydrogen or a non-proton donative Lewis basic functional group and an electron attractive group. The particles(a) used herein are dry and substantially contain no water, and substantially forms no aluminoxane by contact with trialkylaluminum.
As the particles(a), there can be preferably used those which are generally used as a carrier. A porous substance having a uniform particle diameter is preferred and an inorganic substance or an organic polymer is preferably used.
Examples of the inorganic substance which can be used as the particles(a) in the present invention include inorganic oxides and magnesium compounds, and clays and clay minerals can also be used unless no problem arises. These inorganic substances may be used in combination.
Specific examples of the inorganic oxide include SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2 and mixtures thereof such as SiO2xe2x80x94MgO, SiO2xe2x80x94Al2O3, SiO2xe2x80x94TiO2, SiO2xe2x80x94V2O5, SiO2xe2x80x94Cr2O3, SiO2xe2x80x94TiO2xe2x80x94MgO, etc. Among these inorganic oxides, SiO2 and/or Al2O3 are preferred. The above inorganic oxide may contain a small amount of carbonate, sulfate, nitrate and oxide components, such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, Li2O, etc.
Examples of the magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride and the like; alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, octoxymagnesium chloride and the like; aryloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride and the like; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium and the like; aryloxymagnesiums such as phenoxymagnesium, di-methylphenoxymagnesium and the like; magnesium carboxylates such as magnesium laurate, magnesium stearate and the like.
Among them, magnesium halides or alkoxymagnesiums are preferred, and magnesium chloride or butoxymagnesium is more preferred.
Examples of the clay or clay mineral include kaolin, bentonite, Kibushi clay, gaerome clay, allophane, hisingerite, pyrophylite, talc, a mica group, a montmorillinite group, vermiculite, a chlorite group, palygorskite, kaolinite, nacrite, dickite, halloycite and the like. Among them, smectite, montmorillinite, hectorite, raponite and saponite are preferred, and montmorillinite and hectorite are more preferred.
It is necessary that these inorganic substances are dried to substantially remove water, and those dried by a heat treatment are preferred. The heat treatment is normally carried out at the temperature of 100 to 1500xc2x0 C., preferably 100 to 1000xc2x0 C., and more preferably 200 to 800xc2x0 C. There can be used a method of passing the heated inorganic substance through a dried inert gas (e.g. nitrogen, argon) at a fixed flow rate for a few hours or more, or a method of evacuating for several hours, but the method is not limited.
The average particle diameter of the inorganic substance is preferably from 5 to 1000 xcexcm, more preferably from 10 to 500 xcexcm, and most preferably from 10 to 100 xcexcm. The pore volume is preferably not less than 0.1 ml/g, and more preferably 0.3 to 10 ml/g. The specific surface area is preferably from 10 to 1000 m2/g, and more preferably from 100 to 500 m2/g.
As the organic polymer used as the particles(a) in the present invention, any organic polymer may be used and a mixture of plural kinds of organic polymer may also be used. As the organic polymer, an organic polymer having a functional group capable of reacting with the organometallic compound(b) is preferred. Examples of the functional group include functional group containing active hydrogen and a non-proton donative Lewis basic functional group. As the organic polymer which can be used as the particles(a), a polymer having a functional group containing active hydrogen or a non-proton donative Lewis basic functional group is preferred.
The functional group containing active hydrogen may be any one containing an active hydrogen, and is not specifically limited. Specific examples thereof include a primary amino group, secondary amino group, imino group, amide group, hydrazide group, amidino group, hydroxy group, hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid group, sulfinic acid group, sulfenic acid group, thiol group, thioformyl group, pyrrolyl group, imidazolyl group, piperidyl group, indazolyl group, carbazolyl group and the like. Among them, a primary amino group, secondary amino group, imino group, amide group, hydroxy group, formyl group, carboxyl group, sulfonic acid group or thiol group is preferred. A primary amino group, secondary amino group, imino group, amide group or hydroxy group is particularly preferred. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
The non-proton donative Lewis basic functional group may be any functional group having a Lewis basic portion containing no active hydrogen atom, and is not specifically limited. Specific examples thereof include pyridyl group, N-substituted imidazolyl group, N-substituted indazolyl group, nitrile group, azido group, N-substituted imino group, N,N-substituted amino group, N,N-substituted aminoxy group, N,N,N-substituted hydrazino group, nitroso group, nitro group, nitroxy group, furyl group, carbonyl group, thiocarbonyl group, alkoxy group, alkyloxycarbonyl group, N,N-substituted carbamoyl group, thioalkoxy group, substituted sulfinyl group, substituted sulfonyl group, substituted sulfonic acid group and the like. A heterocyclic group is preferred, and an aromatic heterocyclic group having an oxygen atom and/or a nitrogen atom in the ring is more preferred. Among them, pyridyl group, N-substituted imidazolyl group and N-substituted indazoyl groups are particularly preferred and pyridyl group is most preferred. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
The amount of the functional group containing active hydrogen or non-proton donative Lewis basic functional group is not specifically limited, but is preferably from 0.01 to 50 mmol/g, and more preferably from 0.1 to 20 mmol/g, in terms of a molar amount of the functional group per g of the organic polymer.
The organic polymer having said functional group can be obtained, for example, by polymerizing a monomer having a functional group containing active hydrogen or a non-proton donative Lewis basic functional group, or this monomer and another monomer. At this time, it is preferred to copolymerize the above monomers with a crosslinking polymerizable monomer having two or more polymerizable unsaturated bonds.
Examples of the monomer having a functional group containing active hydrogen or a non-proton donative Lewis basic functional group include the above monomer having a functional group containing active hydrogen, and a polymerizable unsaturated group or monomer having a functional group having a Lewis basic portion containing no active hydrogen, and a polymerizable unsaturated group.
Examples of the polymerizable unsaturated group include alkenyl groups such as vinyl group, allyl group and the like; alkynyl groups such as ethyne group and the like. Examples of the monomer having a functional group containing active hydrogen and a polymerizable unsaturated group include a vinyl group-containing primary amine, vinyl group-containing secondary amine, vinyl group-containing amide compound and vinyl group-containing hydroxy compound. Specific examples thereof include N-(1-ethenyl)amine, N-(2-propenyl)amine, N-(1-ethenyl)-N-methylamine, N-(2-propenyl)-N-methylamine, 1-ethenylamide, 2-propenylamide, N-methyl-(1-ethenyl)amide, N-methyl-(2-propenyl)amide, vinyl alcohol, 2-propen-1-ol, 3-buten-1-ol and the like.
Specific examples of the monomer having a functional group having a Lewis basic portion containing no active hydrogen, and a polymerizable unsaturated group include vinylpyridine, vinyl(N-substituted)imidazole and vinyl(N-substituted)indazole.
The other monomers having a polymerizable unsaturated group include ethylene, xcex1-olefin and the like, and specific examples thereof include ethylene, propylene, butene-1, hexene-1, 4-methyl-pentene-1, styrene and the like. Among them, ethylene or styrene is preferred. Two or more kinds of these monomers may be used.
Specific examples of the crosslinking polymerizable monomer having two or more polymerizable unsaturated groups include divinylbenzene and the like.
The average particle diameter of the organic polymer is preferably from 5 to 1000 xcexcm, and more preferably from 10 to 500 xcexcm. The pore volume is preferably not less than 0.1 ml/g, and more preferably 0.3 to 10 ml/g. The specific surface area is preferably from 10 to 1000 m2/g, and more preferably from 50 to 500 m2/g.
(b) Organometallic Compound
The organometallic compound (b) used in the present invention is an organometallic compound represented by the following general formula (1):
R1nAXqxe2x88x92nxe2x80x83xe2x80x83(1)
(wherein A represents a metal atom of the 2nd, 12th or 13th Group of the Periodic Table of Element(IUPAC 1993); R1 represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbonoxy group having 1 to 20 carbon atoms and a plurality of R1 may be the same or different; X represents a halogen atom or a hydrogen atom; n represents a number satisfying the expression 0 less than nxe2x89xa6q; and q is a valence number of the metal atom.).
A above preferably includes a boron atom, aluminum atom, magnesium atom, zinc atom and the like. When A is a boron atom or aluminum atom, the valence number is 3 (q=3)m, and when A is magnesium atom or zinc atom, the valence number is 2(q=2). When A is a boron atom, R1 is preferably the hydrocarbon group described above, and specific examples of thereof include trialkylboranes such as trimethylborane, triethylborane, tripropylborane, tributylborane, triphenylborane and the like; dialkylhalidoboranes such as dimethylchloroborane, diethylchloroborane, dipropylchloroborane, dibutylchloroborane, diphenylchloroborane and the like; dialkylhydrideborane such as dimethylhydridoborane, diethylhydridoborane, dipropyldihydridoborane, dibutylhydridoborane, diphenylhydridoborane and the like; alkyldihalideborane such as methyldichloroborane, ethyldichloroborane, propyldichloroborane, butyldichloroborane, phenyldichloroborane and the like.
When A is an aluminum atom, R1 is preferably the hydrocarbon group described above, and specific examples of thereof include trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum and the like; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum halide, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride and the like; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminumdichloride, n-butylaluminumdichloride, isobutylaluminum dichloride, n-hexylaluminum dichloride and the like; dialkylaluminumhydrides such as dimethylaluminumhydride, diethylaluminumhydrido, di-n-propylaluminumhydride, diisopropylaluminumhydride, di-n-butylaluminumhydride, diisobutylaluminumhydride, di-n-hexylaluminumhydride and the like.
Trialkylaluminums are preferred, and trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum and tri-n-hexylaluminum are more preferred. Among them, trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferred.
When A is a magnesium atom, R1 is preferably the hydrocarbon group described above, and specific examples of thereof include diethylmagnesium, di-n-butylmagnesium and the like, and there is also included di-n-butoxymagnesium in which R1 is the hydrocarbonoxy group described above. And, when A is a zinc atom, R1 is preferably the hydrocarbon group described above, and specific examples of thereof include diethylzinc and the like.
The organometallic compound(b) is more preferably an organoaluminum compound and organoboron compound, and an organoaluminum compound is most preferred.
(c) Compound Having a Functional Group Containing Active Hydrogen or a Non-proton Donative Lewis Basic Functional Group, and an Electron Attractive Group
The functional group containing active hydrogen or non-proton donative Lewis basic functional group of the compound(c) used in the present invention normally reacts with the organometallic compound.
The functional group containing active hydrogen and non-proton donative Lewis basic functional group are the same as those described herein-above.
The compound(c) has an electron attractive group, but a substituent constant "sgr" of Hammett""s rule can be used as an index of the electron attractive group. A functional group wherein the substituent constant "sgr" of Hammett""s rule is positive corresponds to the electron attractive group.
Specific examples of the electron attractive group include a fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, phenyl group, acetyl group, carbonyl group, thionyl group, sulfone group, carboxyl group and the like.
In the compound(c), a functional group containing active hydrogen and a non-proton donative Lewis basic functional group may be the same. And, the compound(c) may have plural kinds and/or a plurality of functional groups containing active hydrogen or non-proton donative Lewis basic functional groups, and electron attractive groups. Examples of the compound(c) include amines, phosphines, alcohols, phenols, thiols, thiophenols, carboxylic acids and sulfonic acids, having an electron attractive group, and the like.
The compound (c) is preferably a compound represented by the following general formula (2):
R2mZHzxe2x88x92mxe2x80x83xe2x80x83General formula (2)
(wherein R2 represents an electron attractive group or a group containing an electron attractive group; Z represents an atom of the 15th or 16th Group of the Periodic Table; H represents a hydrogen atom; and z represents a valence of Z, provided m is 1 when z is 2 and m is 1 or 2 when z is 3).
Examples of the group containing an electron attractive group in R2 of the general formula (2) include a halogenated alkyl group, halogenated aryl group, cyanated aryl group, nitrated aryl group, ester group and the like.
Specific examples of the halogenated alkyl group include fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, diiodomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-tribromoethyl group, 2,2,2-triiodoethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,3,3,3-pentabromopropyl group, 2,2,3,3,3-pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 2,2,2-trichloro-1-trichloromethylethyl group, 2,2,2-tribromo-1-tribromomethylethyl group, 2,2,2-triiodo-1-triiodomethylethyl group, 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl group, 1,1,3,3,3-hexachloro-2-trichloromethylpropylgroup, 1,1,3,3,3-hexabromo-2-tribromomethylpropyl group, 1,1,3,3,3-hexaiodo-2-triiodomethylpropyl group and the like.
Specific examples of the halogenated aryl group include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 2,6-dichlorophenyl group, 3,5-dichlorophenyl group, 2,6-dibromophenyl group, 3,5-dibromophenyl group, 2,6-diiodophenyl group, 3,5-diiodophenyl group, 2,4,6-trifluorophenyl group, 2,4,6-trichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-triiodophenyl group, pentafluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentaiodophenyl group, 2-(trifluoromethyl)phenyl group, 3-(trifluoromethyl)phenyl group, 4-(trifluoromethyl)phenyl group, 2,6-di(trifluoromethyl)phenyl group, 3,5-di(trifluoromethyl)phenyl group, 2,4,6-tri(trifluoromethyl)phenyl group and the like.
Specific examples of the cyanated aryl group include 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group and the like.
Specific examples of the nitrated aryl group include 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group and the like.
Specific examples of the ester group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, pentafluorophenyloxycarbonyl group and the like.
R2 of the general formula (2) is preferably a halogenated alkyl or halogenated aryl group, more preferably a fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoromethyl group, 2,2,3,3,3-pentafluoromethyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl group, 4-fluorophenyl group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group or pentafluorophenyl group, more preferably a trifluoromethyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl group or pentafluorophenyl group.
Z in the general formula (2) represents an atom of the 15th or 16th Group of the Periodic Table, and H represents a hydrogen atom. Specific examples of Z include a nitrogen atom, phosphorus atom, oxygen atom, sulfur atom and the like. Among them, a nitrogen atom or oxygen atom is preferred and an oxygen atom is more preferred.
z represents a valence of Z. For example, z is 3 when Z is a nitrogen atom or a phosphorus atom, whereas, z is 2 when Z is am oxygen atom or a sulfur atom. m is 1 when z is 2, whereas, m is 1 or 2 when z is 3.
Specific examples of the amines described as for the compound(c) include di(fluoromethyl)amine, di(chloromethyl)amine, di(bromomethyl)amine, di(iodomethyl)amine, di(difluoromethyl)amine, di(dichloromethyl)amine, di(dibromomethyl)amine, di(diiodomethyl)amine, di(trifluoromethyl)amine, di(trichloromethyl)amine, di(tribromomethyl)amine, di(triiodomethyl)amine, di(2,2,2-trifluoroethyl)amine, di(2,2,2-trichloroethyl)amine, di(2,2,2-tribromoethyl)amine, di(2,2,2-triiodoethyl)amine, di(2,2,3,3,3-pentafluoroopropyl)amine, di(2,2,3,3,3-pentachloropropyl)amine, di(2,2,3,3,3-pentabromopropyl)amine, di(2,2,3,3,3-pentaiodopropyl)amine, di(2,2,2-trifluoro-1-trifluoromethylethyl)amine, di(2,2,2-trichloro-1-trichloromethylethyl)amine, di(2,2,2-tribromo-1-tribromomethylethyl)amine, di(2,2,2-triiodo-1-triiodomethylethyl)amine, di(1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl)amine, di(1,1,1,3,3,3-hexachloro-2-trichloromethylpropyl)amine, di(1,1,1,3,3,3-hexabromo-2-tribromomethylpropyl)amine, di(1,1,1,3,3,3-hexaiodo-2-triiodomethylpropyl)amine, di(2-fluorophenyl)amine, di(3-fluorophenyl)amine, di(4-fluorophenyl)amine, di(2-chlorophenyl)amine, di(3-chlorophenyl)amine, di(4-chlorophenyl)amine, di(2-bromophenyl)amine, di(3-bromophenyl)amine, di(4-bromophenyl)amine, di(2-iodophenyl)amine, di(3-iodophenyl)amine, di(4-iodophenyl)amine, di(2,6-difluorophenyl)amine, di(3,5-difluorophenyl)amine, di(2,6-dichlorophenyl)amine, di(3,5-dichlorophenyl)amine, di(2,6-dibromophenyl)amine, di(3,5-dibromophenyl)amine, di(2,6-diiodophenyl)amine, di(3,5-diiodophenyl)amine, di(2,4,6-trifluorophenyl)amine, di(2,4,6-trichlorophenyl)amine, di(2,4,6-tribromophenyl)amine, di(2,4,6-triiodophenyl)amine, di(pentafluorophenyl)amine, di(pentachlorophenyl)amine, di(pentabromophenyl)amine, di(pentaiodophenyl)amine, di(2-(trifluoromethyl)phenyl)amine, di(3-(trifluoromethyl)phenyl)amine, di(4-(trifluoromethyl)phenyl)amine, di(2,6-di(trifluoromethyl)phenyl)amine, di(3,5-di(trifluoromethyl)phenyl)amine, di(2,4,6-tri(trifluoromethyl)phenyl)amine, di(2-cyanophenyl)amine, di(3-cyanophenyl)amine, di(4-cyanophenyl)amine, di(2-nitrophenyl)amine, di(3-nitrophenyl)amine, di(4-nitrophenyl)amine and the like. There can also be exemplified phosphine compounds wherein the nitrogen atom is replaced with a phosphorous atom. Those phosphine compounds are compounds represented by replacing amine of the above specific examples with phosphine.
Specific examples of the alcohols described as for the compound(c) include fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodomethanol, trifluoromethanol, trichloromethanol, tribromomethanol, triiodomethanol, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2,2,2-tribromoethanol, 2,2,2-triiodoethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,3,3,3-pentachloropropanol, 2,2,3,3,3-pentabromopropanol, 2,2,3,3,3-pentaiodopropanol, 2,2,2-trifluoro-1-trifluoromethylethanol, 2,2,2-trichloro-1-trichloromethylethanol, 2,2,2-tribromo-1-tribromomethylethanol, 2,2,2-triiodo-1-triiodomethylethanol, 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol, 1,1,1,3,3,3-hexachloro-2-trichloromethylpropanol, 1,1,1,3,3,3-hexabromo-2-tribromomethylpropanol, 1,1,1,3,3,3-hexaiodo-2-triiodomethylpropanol and the like. There can also be exemplified thiol compounds wherein the oxygen atom is replaced with a sulfur atom. Those thiol compounds are compounds represented by replacing methanol of the above specific examples with methanethiol, replacing ethanol with ethanethiol and replacing propanol with propanethiol, respectively, and the like.
Specific examples of the phenols described as for the compound(c) include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,6-dichlorophenol, 3,5-dichlorophenol, 2,6-dibromophenol, 3,5-dibromophenol, 2,6-diiodophenol, 3,6-diiodophenol, 2,4,6-trifluorophenol, 2,4,6-trichlorophenol, 2,4,6-tribromophenol, 2,4,6-triiodophenol, pentafluorophenol, pentachlorophenol, pentabromophenol, pentaiodophenol, 2-(trifluoromethyl)phenol, 3-(trifluoromethyl)phenol, 4-(trifluoromethyl)phenol, 2,6-di(trifluoromethyl)phenol, 3,5-di(trifluoromethyl)phenol, 2,4,6-tri(trifluoromethyl)phenol, 2-cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol and the like. There can also be exemplified thiophenol compounds wherein the oxygen atom is substituted with a sulfur atom. Those thiophenol compounds are compounds represented by substituting phenol of the above specific examples with thiophenol.
Specific examples of the carboxylic acids described as for the compound(c) include 2-fluorobenzoic acid, 3-fluorobenzoic acid, 4-fluorobenzoic acid, 2,3-difluorobenzoic acid, 2,4-difluorobenzoic acid, 2,5-difluorobenzoic acid, 2,6-difluorobenzoic acid, 2,3,4-trifluorobenzoic acid, 2,3,5-trifluorobenzoic acid, 2,3,6-trifluorobenzoic acid, 2,4,5-trifluorobenzoic acid, 2,4,6-trifluorobenzoic acid, 2,3,4,5-tetrafluorobenzoic acid, 2,3,4,6-tetrafluorobenzoic acid, pentafluorobenzoic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoroethylcarboxylic acid, heptafluoropropylcarboxylic acid, 1,1,1,3,3,3-hexafluoro-2-propylcarboxylic acid and the like.
Specific examples of the sulfonic acids as for the compound(c) include fluoromethanesulfonic acid, difluoromethanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, 1,1,1,3,3,3-hexafluoro-2-propanesulfonic acid and the like.
Preferred examples of the amines as for the compound(c) include di(trifluoromethyl)amine, di(2,2,2-trifluoroethyl)amine, di(2,2,3,3,3-pentafluoropropyl)amine, di(2,2,2-trifluoro-1-trifluoromethylethyl)amine, di(1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl)amine and di(pentafluorophenyl)amine; preferred examples of the alcohols include trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1-trifluoromethylethanol and 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol; preferred examples of the phenols include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, pentafluorophenol, 2-(trifluoromethyl)phenol, 3-(trifluoromethyl)phenol, 4-(trifluoromethyl)phenol, 2,6-di(trifluoromethyl)phenol, 3,5-di(trifluoromethyl)phenol and 2,4,6-tri(trifluoromethyl)phenol; preferred examples of the carboxylic acids include pentafluorobenzoic acid and trifluoroacetic acid; and preferred examples of the sulfonic acids include trifluoromethanesulfonic acid.
More preferred examples of the compound(c) include di(trifluoromethyl)amine, di(pentafluorophenyl)amine, trifluoromethanol, 2,2,2-trifluoro-1-trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol, 4-fluorophenol, 2,6-difluorophenol, 2,4,6-trifluorophenol, pentafluorophenol, 4-(trifluoromethyl)phenol, 2,6-di(trifluoromethyl)phenol and 2,4,6-tri(trifluoromethyl)phenol, more preferably pentafluorophenol or 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol (common use name: perfluoro-tert-butanol).
(A) Modified Particles
The modified particles of the present invention is obtained by contacting dry particles(a) with an organometallic compound(b), and then a compound(c) having a functional group containing active hydrogen or a non-proton donative Lewis basic functional group and an electron attractive group.
It is preferable that the contact treatment of (a) with (b), and subsequent contact treatment with (c) are carried out under an inert gas atmosphere.
The treating temperature is normally within the range from xe2x88x9280 to 200xc2x0 C., preferably from xe2x88x9220 to 150xc2x0 C., and more preferably from 0 to 100xc2x0 C. The treating time is normally from 1 minute to 48 hours, and preferably from 10 minutes to 24 hours. It is preferred to use a solvent and the solvent used is preferably an aliphatic or aromatic hydrocarbon solvent, which is inert to (a), (b) and (c). Examples of the aliphatic hydrocarbon solvent include butane, pentane, hexane, heptane, octane and the like; and examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and the like. There can also be used those obtained by optionally mixing these hydrocarbon solvents.
In the case of the contact of (a) with (b), and the subsequent contact with (c), the method of contacting (a) with (b), and the method of the following contacting with (c) may be the same or different.
The contact treated particles in each contacting step may be not subjected to isolation operation, but it is preferable to isolate each the treated particles after each of contact of (a) with (b), and contact of thus contact-treated particles with (c), respectively. As examples of the isolating method, there can be included a method of decantation of the supernatant of the reaction solution, method of washing the treated particles with an inert solvent after filtration, method of washing the treated particles with an inert solvent after filtration and drying them under reduced pressure or an inert gas flow, method of distilling off the solvent of the reaction solution under reduced pressure or an inert gas flow, and the like. Alternatively, when the isolation of the treated particles obtained as described above is not conducted, the particles obtained in the reaction liquid may be used in the polymerization in a state of being suspended in the inert solvent.
Regarding the amount of (b) to (a) in the preparation of the modified particles of the present invention, the metal atom of the organometallic compound(b) contained in the particles obtained by contacting (a) with (b) is preferably not less than 0.1 mmol, and more preferably 0.5 to 20 mmol, in terms of the number of mol of the metal atom contained in 1 g of the particles in the dry state. Regarding the amount of (c), the molar ratio of the compound(c) having a functional group containing active hydrogen or a non-proton donative Lewis basic functional group, and an electron attractive group to the organometallic compound (b) contained in 1 g of particles in the dry state, i.e. (c)/(b), is preferably from 0.01 to 100, more preferably from 0.05 to 5, and most preferably from 0.1 to 2.
The modified particles of the present invention can be used as a carrier for supporting a catalyst component for olefin polymerization, such as a transition metal compound, and is suitably used in the polymerization accompanying formation of polymer particles. The modified particles of the present invention can functions as a catalyst component for olefin polymerization. Examples of the catalyst for olefin polymerization using the modified particles of the present include those obtained by using modified particles(A) and a transition metal compound(B), and those obtained using modified particles(A), a transition metal compound(B) and an organometallic compound(C).
(B) Transition Metal Compound
The transition metal compound used in the present invention may be any transition metal compound having olefin polymerization activity, and the transition metal is preferably a transition metal of the 4th Group or lanthanide series of the Periodic Table of the Elements (1993, IUPAC). The transition metal compound is a metallocene transition metal compound, more preferably.
The metallocene transition metal compound is, for example, a compound represented by the following general formula (3):
MLaR3pxe2x88x92axe2x80x83xe2x80x83(3)
(wherein M represents a transition metal of the 4th Group or lanthanide series of the Periodic Table of the Elements (1993, IUPAC); L represents a group having a cyclopentadiene type anion skeleton or a group having a hetero atom, at least one of which is a group having a cyclopentadiene type anion skeleton, and a plurality of L may be the same or different and may be crosslinked each other; R3 represents a hydrocarbon group having 1 to 20 carbon atoms; a represents a number satisfying the expression 0 less than axe2x89xa6p; and p represents a valence of a transition metal atom M).
In the general formula (3) representing the metallocene transition metal compound, M is a transition metal of the 4th Group or lanthanide series of the Periodic Table of the Elements (1993, IUPAC). Specific examples of the transition metal of the 4th Group include titanium atom, zirconium atom, hafnium atom and the like; and examples of the transition metal atom of lanthanide series include samarium and the like. Among them, titanium atom, zirconium atom or hafnium atom is preferred.
In the general formula (3) representing the metallocene transition metal compound, L is a group having a cyclopentadiene type anion skeleton or a group having a hetero atom, at least one of which is a group having a cyclopentadiene type anion skeleton. A plurality of L may be the same or different and may be crosslinked each other. Examples of the a group having a cyclopentadiene type anion skeleton include xcex75-cyclopentadienyl group, xcex75-substituted-cyclopentadienyl or polycyclic group having a cyclopentadiene type anion skeleton. Examples of the substituent of the xcex75-substituted cyclopentadienyl group include hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms or silyl group having 1 to 20 carbon atoms. Examples of the polycyclic group having a cyclopentadiene form anion skeleton include xcex75-indenyl group, xcex75-fluorenyl group and the like.
Examples of the hetero atom in the group having a hetero atom include a nitrogen atom, phosphorus atom, oxygen atom, sulfur atom and the like. Examples of the group having such a hetero atom include hydrocarbon amino group, hydrocarbon phosphino group, hydrocarbon oxy group, hydrocarbon thio group and the like, and preferred examples thereof include alkoxy group, aryloxy group, alkylthio group, arylthio group, dialkylamino group, diarylamino group, dialkylphosphino group or diarylphosphino group.
Specific examples of the xcex75-substituted-cyclopentadienyl group include xcex75-methylcyclopentadienyl group, xcex75-ethylcyclopentadienyl group, xcex75-n-propylcyclopentadienyl group, xcex75-isopropylcyclopentadienyl group, xcex75-n-butylcyclopentadienyl group, xcex75-isobutylcyclopentadienyl group, xcex75-sec-butylcyclopentadienyl group, xcex75-tert-butylcyclopentadienyl group, xcex75-1,2-dimethylcyclopentadienyl group, xcex75-1,3-dimethylcyclopentadienyl group, xcex75-1,2,3-trimethylcyclopentadienyl group, xcex75-1,2,4-trimethylcyclopentadienyl group, xcex75-teramethylcyclopentadienyl group, xcex75-pentamethylcyclopentadienyl group, xcex75-trimethylsilylcyclopentadienyl group and the like.
Specific examples of the polycyclic group having a cyclopentadiene type anion skeleton include xcex75-indenyl group, xcex75-2-methylindenyl group, xcex75-4-methylindenyl group, xcex75-4,5,6,7-tetarhydroindenyl group, xcex75-fluorenyl group and the like.
Specific examples of the group having a hetero atom include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, thiomethoxy group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, diphenylamino group, pyrrolyl group, dimethylphisphino group and the like.
Groups having a cyclopentadiene type anion skeleton, or a group having a cylopentadienyl group and a group having a hetero atom may be crosslinked. In that case, an alkylene group such as ethylene group, propylene group or the like, a substituted alkylene group such as dimethylmethylene group, diphenylmethylene group or the like, or a substituted silylene group such as silylene group, dimethylsilylene group, diphenylsilylene group, tetramethyldisilylene group or the like may be lie therebetween.
R3 in the general formula (3) representing the metallocene transition metal compound is a halogen atom or a hydrocaron group having 1 to 20 carbon atoms a is a number satisfying the expression 0 less than axe2x89xa6p and p is a valence of a transition metal atom M). Specific examples of R3 include halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom or the like; and hydrocarbon group having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group and the like. Preferred examples of R3 include chlorine atom, methyl group or benzyl group.
Among the metallocene transition metal compounds represented by the above general formula (3), specific examples of the compound wherein the transition metal atom M is a zirconium atom, include bis(cyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(1,3-dimethylcyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, bis(fluorenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, ethylenebis(2-methylindenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, dimethylsilylenebis(cyclopentadienyl)zirconium dichloride, dimethylsilylenebis(indenyl)zirconium dichloride, dimethylsilylenebis(2-methylindenyl)zirconium dichloride, dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, dimethylsilylenebis(cyclopentadienyl)(fluorenyl)zirconium dichloride, diphenylsilylenebis(indenyl)zirconium dichloride, (cyclopentadienyl)(dimethylamide)zirconium dichloride, (cyclopentadienyl)(phenoxy)zirconium dichloride, dimethylsilylene(tert-butylamide)(tetramethylcyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)zirconium dimethyl, bis(methylcyclopentadienyl)zirconium dimethyl, bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(indenyl)zirconium dimethyl, bis(4,5,6,7-tetrahydroindenyl)zirconium dimethyl, bis(fluorenyl)zirconium dimethyl, ethylenebis(indenyl)zirconium dimethyl, dimethylsilylene(tert-butylamide)(tetramethylcyclopentadienyl)zirconium dimethyl and the like.
There can also be exemplified compounds wherein zirconium is replaced with titanium or hafnium in the above zirconium compounds.
These metallocene transition metal compounds may be used alone or in combination thereof.
(C) Organoaluminum Compound
As the organoaluminum compound(C) used in the present invention, a publicly known organoaluminum compound can be used. Preferably, it is an organoaluminum compound represented by the general formula (4) R4bAlY3xe2x88x92b (wherein R4 represents a hydrocarbon group having 1 to 8 carbon atoms; Al represents an aluminum atom; Y represents a hydrogen atom and/or halogen atom; and b represents a number satisfying 0 less than bxe2x89xa63).
Specific examples of R4 in the general formula (4) representing the organoaluminum compound include a methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group, 2-methylhexyl group, n-octyl group and the like. Among them, an ethyl group, n-butyl group, isobutyl group and n-hexyl group are preferred. Specific examples of the halogen atom as for Y include fluorine atom, chlorine atom, bromine atom and iodine atom, preferably a chlorine atom.
Specific examples of the organoaluminum compound represented by the general formula (4) R4bAlY3xe2x88x92b include trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like; dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride and the like; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, n-hexylaluminum dichloride and the like; dialkylaluminum hydride such as dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, di-n-hexylaluminum hydride and the like. Among them, trialkylaluminums are preferred, and trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum and tri-n-hexylaluminum are more preferred and triisobutylaluminum and tri-n-hexylaluminum are most preferred.
These organoaluminum compounds may be used alone or in combination thereof.
The catalyst for olefin polymerization of the present invention comprises modified particles (A) and a transition metal compound(B) and optionally an organometallic compound(C). The amount of the component(B) is normally from 1xc3x9710xe2x88x926 to 1xc3x9710xe2x88x923 mol, and preferably from 5xc3x9710xe2x88x926 to 5xc3x9710xe2x88x924 mol, per 1 g of the component(A). And, the amount of the organometallic compound as the component(C) is preferably from 0.01 to 10,000, more preferably from 0.1 to 5,000, and most preferably from 1 to 2,000 in terms of molar ratio of the metal atom of the organometallic compound as the compound(c) to the transition metal atom of the transition metal compound as the component(B), i.e. (C)/(B).
In the present invention, the component(A) and component(B) and optionally component(C) can be charged in a reactor in an arbitrary order at the time of polymerization. Alternatively, these arbitrary components in an arbitrary combination may be charged in the reactor after previously bringing into contact with each other.
As a monomer used in the polymerization in the present invention, any olefins and diolefins, having 2 to 20 carbon atoms, etc. can be used. Two or more olefins can also be used, simultaneously. The monomers are exemplified blow, but the present invention is not to the compounds described below. Specific examples of the olefin include xcex1-olefins having 3 to 20 hydrocarbon atoms such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene1, 4-methyl-1-pentene and the like, and olefins such as vinylcyclohexane and the like. Diolefins include conjugated dienes and non-conjugated dienes, and specific examples of the compounds include 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene and the like as a non-conjugated diene, and 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene and the like as a conjugated diene.
As a combination of monomers constituting a copolymer, combinations of ethylene and xcex1-olefins described above (for example, ethylene and propylene, ethylene and butene-1, ethylene and hexene-1) are preferable, and further, combinations of xcex1-olefins (for example, propylene and butene-1 and the like) are also exemplified, but the present invention should not be limited to the above compounds.
In the present invention, an aromatic vinyl compound can also be used as the monomer. Specific examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, divinylbenzene and the like.
The polymerization method is not particularly limited, and there can be used gas phase polymerization in a gaseous monomer, solution polymerization using a solvent, slurry polymerization or the like. Examples of the solvent used in the solution polymerization or slurry polymerization include aliphatic hydrocarbon solvents such as butane, pentane, heptane, octane and the like; aromatic hydrocarbon solvents such as benzene, toluene and the like; halogenated hydrocarbon solvents such as methylene chloride and the like. It is also possible to use the olefin itself as the solvent. The polymerization method may be batch-wise polymerization or continuous polymerization and, furthermore, the polymerization may be performed in two or more stages under different reaction conditions, respectively. The polymerization time is appropriately determined according to the kind of the desired olefin polymer and reaction apparatus, but can be within the range from 1 minute to 20 hours.
The present invention can be applied to the polymerization accompanying formation of polymer particles (e.g. slurry polymerization, gas phase polymerization, etc.), particularly preferably.
The slurry polymerization may be performed according to a publicly known slurry polymerization method and polymerization conditions.
According to the preferred polymerization method in the slurry method, there is used a continuous type reactor wherein a monomer (comonomer), a feed and a diluent are optionally added and a polymer product is taken out, continuously or periodically. As the reactor, there is used a loop reactor or a plurality of stirring reactors, having different reactors or reaction conditions, connected in series or parallel or a combination thereof
As the diluent, there can be used an inert diluent (medium) such as a paraffin, cycloparaffin or aromatic hydrocarbon. The temperature of the polymerization reactor or reaction zone is normally within the range from about 50 to about 100xc2x0 C., and preferably from 60 to 80xc2x0 C. The pressure can normally vary within the range from about 0.1 to about 10 MPa, and preferably from 0.5 to 5 MPa. There can be set to the pressure at which a catalyst can be maintained in the suspended state and a medium and at least a part of a monomer and a comonomer can be maintained in the sate of a liquid phase and, furthermore, the monomer and comonomer can be contacted therewith. Accordingly, the medium, temperature and pressure may be selected so that the olefin polymer is formed as solid particles and is recovered in that form.
The molecular weight of the olefin polymer can be controlled by publicly known means such as control of the temperature of the reaction zone, introduction of hydrogen or the like.
The respective catalyst components and monomer (and comonomer) can be added to the reactor or reaction zone by a publicly known arbitrary method in arbitrary order. For example, there can be used a method of adding the respective catalyst components and monomer (and comonomer) to the reaction zone, simultaneously or successively. If desired, the respective catalyst components can be previously contacted with each other in an inert atmosphere prior to contact with the monomer (and comonomer).
The gas phase polymerization may be performed according to a publicly known gas phase polymerization method and polymerization conditions, but is not limited thereto. As the gas phase polymerization apparatus, there can be used a fluidized bed type reactor, preferably a fluidized bed type reactor having an extended portion. A reaction apparatus equipped with a stirring blade in a reactor may also be used with no problem.
As the method of feeding the respective components to the polymerization reactor, there can be used a method of feeding them in the absence of water using an inert gas (e.g. nitrogen, argon), hydrogen, ethylene or the like, or a method of feeding them in the form of a solution or slurry dissolved or diluted in a solvent. The respective catalyst components may be separately fed, or fed after previously contacting the arbitrary components with each other in an arbitrary order.
Regarding the polymerization conditions, the temperature is lower than the temperature at which the polymer is molten, preferably from 20 to 100xc2x0 C., and particularly preferably from 40 to 90xc2x0 C. The pressure is preferably within the range from 0.1 to 5 MPa, and more preferably from 0.3 to 4 MPa. Furthermore, hydrogen may also be added as a molecular weight modifier for the purpose of controlling the melt fluidity of the final product. In case of the polymerization, an inert gas may coexist in a mixed gas.